Substituted (1,4) dioxino (2,3-F) benzoimidazole derivatives and their use in pest control

ABSTRACT

Described herein are new benzimidazole derivatives of the formula ##STR1## in which R represents cyano or the group ##STR2## X 1 , X 2 , X 3  and X 4  are identical or different and represent halogen; 
     Y represents alkyl, alkenyl or alkinyl, each of which is optionally substituted by halogen; or represents optionally substituted phenylalkyl or in each case optionally substituted cycloalkyl and cycloalkenyl; and 
     Z represents hydrogen or halogen, 
     a process for the preparation of these substances, and their use for controlling pests. 
     New intermediates and processes for their preparation.

This application is a divisional of application Ser. No. 08/737,075,filed Oct. 29, 1996, now U.S. Pat. No. 5,648,316 which is a 371 ofPCT/EP95/01500 filed Apr. 20, 1995.

The invention relates to new benzimidazole derivatives, to a process fortheir preparation, and to their use as pesticides. The inventionfurthermore also relates to new intermediates and processes for theirpreparation.

It has been disclosed that certain benzimidazole derivatives such as,for example, 2-cyano-3-dimethylaminosulfonyl-6,6,7,7-tetrafluoro-1,4!dioxino 2,3,-f!benzimidazole or2-cyano-6,6-difluoro-2-dimethylaminosulfonyl- 1,3!dioxolo4,5-f!benzimidazole, have fungicidal, or fungicidal and acaricidal,properties (cf. EP-A 0 517 476 and DE-OS (German PublishedSpecification) 4 139 950). However, the efficacy of these prior-artcompounds is not entirely satisfactory in all sorts of application, inparticular when low rates are applied.

There have now been found new benzimidazole derivatives of the formula##STR3## where R represents cyano or the group ##STR4## X¹, X², X³ andX⁴ are identical or different and represent halogen;

Y represents alkyl, alkenyl or alkinyl, each of which is optionallysubstituted by halogen; or represents optionally substitutedphenylalkyl, or in each case optionally substituted cycloalkyl andcycloalkenyl; and

Z represents hydrogen or halogen.

Depending on the nature of the substituents, the compounds of theformula (I) can exist as geometrical and/or optical isomers or variouslycomposed isomer mixtures. The invention relates to the pure isomers andto the isomer mixtures.

In formula (I), the broken line represents a double bond between one ofthe two nitrogen atoms and the adjacent carbon atom which has attachedto it the substituent R. The nitrogen atom which does not participate inthe double bond has attached to it in each case the --SO₂ --Y radical.

Furthermore, it has been found that benzimidazole derivatives of theformula (I) are obtained when benzimidazoles of the formula ##STR5##where R, X¹, X², X³, X⁴ and Z have the abovementioned meaning arereacted with sulphonyl chlorides of the formula

    Cl--SO.sub.2 --Y                                           (III)

in which

Y has the abovementioned meaning,

if appropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary.

Furthermore, it has been found that benzimidazole derivatives of theformula (I) are highly suitable for use as pesticides. They aredistinguished, in particular, by a potent fungicidal, insecticidal andacaricidal activity.

Surprisingly, the benzimidazole derivatives according to the inventiondisplay a better activity than the prior-art compounds of the mostsimilar constitution.

Formula (I) provides general definition of the compounds according tothe invention.

R preferably represents cyano or the group ##STR6## X¹, X², X³ and X⁴are identical or different and preferably represent fluorine, chlorineor bromine.

Y preferably represents C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl and C₂ -C₆-alkinyl, each of which is optionally monosubstituted topentasubstituted by identical or different halogen substituents; orrepresents phenyl-C₁ -C₄ -alkyl which can be monosubstituted totrisubstituted in the phenyl moiety by identical or differentsubstituents from the series consisting of halogen, C₁ -C₄ -alkyl, C₁-C₄ -halogenoalkyl having 1 to 5 identical or different halogen atoms,C₁ -C₄ -alkoxy and/or C₁ -C₄ -halogenoalkoxy having 1 to 5 identical ordifferent halogen atoms, or represents C₃ -C₇ -cycloalkyl which can bemonosubstituted to trisubstituted by identical or different substituentsfrom the series consisting of halogen, C₁ -C₄ -alkyl and/or C₁ -C₄-halogenoalkyl having 1 to 5 identical or different halogen atoms, orrepresents C₅ -C₇ -cycloalkenyl which can be monosubstituted totrisubstituted by identical or different substituents from the seriesconsisting of halogen, C₁ -C₄ -alkyl and/or C₁ -C₄ -halogenoalkyl having1 to 5 identical or different halogen atoms.

Z preferably represents halogen, fluorine, chlorine or bromine.

R particularly preferably also represents cyano or the group of theformula ##STR7## X¹, X², X³ and X⁴ are identical or different andparticularly preferably represent fluorine, chlorine or bromine.

Y particularly preferably represents C₁ -C₄ -alkyl, C₂ -C₄ -alkenyl andC₂ -C₄ -alkinyl, each of which is optionally monosubstituted topentasubstituted by identical or different fluorine and/or chlorinesubstituents; or represents phenyl-C₁ -C₂ -alkyl which can bemonosubstituted to trisubstituted in the phenyl moiety by identical ordifferent substituents from the series consisting of fluorine, chlorine,bromine, C₁ -C₄ -alkyl, C₁ -C₂ -alkoxy, C₁ -C₂ -halogenoalkyl having 1to 5 fluorine and/or chlorine atoms and C₁ -C₂ -halogenoalkoxy having 1to 5 fluorine and/or chlorine atoms, or represents C₃ -C₇ -cycloalkylwhich can be moriosubstituted to trisubstituted by identical ordifferent substituents from the series consisting of fluorine, chlorine,bromine, C₁ -C₄ -alkyl and/or C₁ -C₂ -halogenoalkyl having 1 to 5fluorine and/or chlorine atoms, or represents C₅ -C₇ -cycloalkenyl whichcan be monosubstituted to trisubstituted by identical or differentsubstituents from the series consisting of fluorine, chlorine, bromine,C₁ -C₄ -alkyl and/or C₁ -C₂ -halogenoalkyl having 1 to 5 fluorine and/orchlorine atoms.

Z particularly preferably represents halogen, fluorine, chlorine orbromine.

R very particularly preferably also represents cyano or the group of theformula ##STR8## X¹, X², X³ and X⁴ are identical or different and veryparticularly preferably represent fluorine, chlorine or bromine.

Y very particularly preferably represents methyl, ethyl, n- or i-propyl,n-, i-, s- or t-butyl, allyl, n- or s-butenyl; propargyl, n- ors-butinyl; methyl, ethyl, allyl, n- or s-butenyl, propargyl and n- ors-butinyl, each of which is monosubstituted to trisubstituted byidentical or different fluorine and/or chlorine substituents; orrepresents benzyl or phenethyl, it being possible for each of theseradicals to be monosubstituted to trisubstituted in the phenyl moiety byidentical or different substituents from the series consisting offluorine, chlorine, bromine, methyl, ethyl, methoxy, trifluoromethyland/or trifluoromethoxy, or represents cyclopropyl, cyclopentyl,cyclohexyl, cyclopentenyl and cyclohexenyl, it being possible for eachof these radicals to be monosubstituted to trisubstituted by identicalor different substituents from the series consisting of fluorine,chlorine, bromine, methyl, n- or i-propyl, chloromethyl, dichloromethyland/or trifluoromethyl.

Z very particularly preferably represents hydrogen, fluorine orchlorine.

As far as this is possible, the hydrocarbon radicals mentioned above inthe definition of the compounds according to the invention, such asalkyl, are in each case straight-chain or branched, also in connectionwith other atoms, such as halogenoalkyl.

Examples of the compounds according to the invention are listed inTables 1 to 6.

                  TABLE 1                                                         ______________________________________                                         ##STR9##                     (I-A)                                           ______________________________________                                    

    ______________________________________                                        Compound No.      Y                                                           ______________________________________                                        1                 C.sub.2 H.sub.5                                             2                 C.sub.3 H.sub.7 -i                                                             ##STR10##                                                  4                 C.sub.3 H.sub.7 -n                                          5                 C.sub.4 H.sub.9 -n                                          6                 CH(CH.sub.3)C.sub.2 H.sub.5                                 7                 CF.sub.3                                                    8                 CH.sub.2 CF.sub.3                                           9                                                                                                ##STR11##                                                  10                                                                                               ##STR12##                                                  ______________________________________                                    

Table 2

Table 2 contains compounds of the formula (I) in which

R═CN, X¹ ═F, X² ═F, X³ ═Cl, X⁴ ═F and

Y has the meanings tabulated in Table 1.

Table 3

Table 3 contains compounds of the formula (I) in which

R═CN, X¹ ═F, X² ═Cl, X³ ═Cl, X⁴ ═F and

Y has the meanings tabulated in Table 1.

Tables 4 to 6

Tables 4 to 6 contain those compounds of the formula (I) in which##STR13## and X¹, X², X³ X⁴ and Y have the meanings tabulated in Tables1 to 3.

If, for example, 2-cyano-6,6,7,7-tetrafluoro- 1,4!dioxino2,3-f!benzimidazole and methanesulphonyl chloride are used as startingmaterials, the course of the reaction of the process according to theinvention can be represented by the following equation: ##STR14##

Formula (II) provides a general definition of the benzimidazolesrequired as starting materials for carrying out the process according tothe invention. In formula (II), R, X¹, X², X³, X⁴ and Z preferably, orparticularly preferably, have those meanings which have already beenmentioned above in connection with the description of the compounds ofthe formula (I) as being preferred, or particularly preferred, for R,X¹, X², X³, X⁴, R and Z.

Some of the benzimidazoles of the formula (II) have been disclosed (cf.EP-A 0 517 476 or DE-OS (German Published Specification) 4 139 950).They can be prepared by reacting phenylenediamines of the formula##STR15## in which X¹, X², X³, X⁴ and Z have the abovementioned meanings

with methyl 2,2,2-trichloroacetimidate, of the formula ##STR16## in thepresence of glacial acetic acid at temperatures between 10° C. and 40°C. and reacting the resulting 2-trichloromethyl-benzimidazoles of theformula ##STR17## in which X¹, X², X³, X⁴ and Z have the abovementionedmeanings

with aqueous ammonia solution in the presence of a diluent, such as, forexample, ethanol, at temperatures between 0° C. and 40° C., and, ifappropriate, reacting the

resulting benzimidazoles of the formula ##STR18## in which X¹, X₂, X₃,X₄ and Z have the abovementioned meanings

with hydrogen disulphide in the presence of a diluent, such as, forexample, ethanol, at temperatures between 10° C. and 100° C., ifappropriate in the presence of an acid-binding agent, such as, forexample, triethylamine.

The compounds of the formulae ##STR19## are new. They can be preparedfollowing the above process by reacting6,7-diamnino-2,3-dichloro-2,3-difluoro- 1,4!-benzodioxane, of theformula ##STR20## with methyl 2,2,2-trichloroacetimidate, of the formula##STR21## in the presence of glacial acetic acid at temperatures between10° C. and 40° C., reacting the resulting6,7-dichloro-6,7-difluoro-2-trichloromethyl- 1,4!-dioxino-2,3-f!-benzimidazole, of the formula ##STR22## with aqueous ammoniasolution in the presence of a diluent, such as, for example, ethanol, attemperatures between 0° C. and 40° C., and, if appropriate, reacting theresulting 2-cyano-6,7-dichloro-6,7-difluoro- 1,4!-dioxino-2,3-f!-benzimidazole, of the formula ##STR23## with hydrogen disulphidein the presence of a diluent, such as, for example, ethanol, attemperatures between 10° C. and 100° C., if appropriate in the presenceof an acid-binding agent, such as, for example, triethylamine.

Some of the phenylenediamines of the formula (IV) have been disclosed(cf. EP-A 0 517 476, DE-OS (German Published Specification) 4 139 950,DE-OS (German Published Specification) 3 621 301 and DE-OS (GermanPublished Specification) 3 605 977) They can be prepared by reacting1,4-benzodioxanes of the formula. ##STR24## in which X¹, X₂, X₃, X₄ andZ have the abovementioned meanings

with a mixture of nitric acid and sulphuric acid (which may alsocomprise oleum) at temperatures between 0° C. and 100° C. and eitherreducing the resulting dinitro-1,4-benzodioxanes of the formula##STR25## in which X¹, X₂, X₃, X₄ and Z have the abovementioned meanings

at temperatures between 50° C. and 100° C., for example using iron inthe presence of aqueous hydrochloric acid and ethanol, or reacting themcatalytically with elemental hydrogen at temperatures between 25° C. and100° C. and under a pressure of between 1 and 100 bar and in thepresence of metals or metal compounds of sub-group VIII of the PeriodicSystem of Table Elements, in particular nickel or palladium, ascatalysts (cf also the preparation examples).

6,7-Diamino-2,3-dichloro-2,3-difluoro- 1,4!-benzodioxane, of the formula##STR26## was hitherto unknown. It can be prepared from the aboveprocess, either by reducing 2,3-dichloro-2,3-difluoro-6,7-dinitro1,4!-benzodioxane, of the formula ##STR27## at temperatures between 50°C. and 100° C., for example using iron in the presence of aqueoushydrochloric acid and ethanol, or reacting them catalytically withelemental hydrogen at temperatures between 25° C. and 100° C. and undera pressure of between 1 and 100 bar and in the presence of metals ormetal compounds of sub-group VIII of the Periodic Table of the Elements,in particular nickel or palladium, as catalysts (cf. also thepreparation examples).

2,3-Dichloro-2,3-difluoro-6,7-dinitro- 1,4!-benzodioxane, of the formula##STR28## was also hitherto unknown. The compound of the formula(VIII-1) can be prepared by reacting 2,3-dichloro-2,3-difluoro-1,4!-benzodioxane, of the formula ##STR29## with a mixture of nitricacid and sulphuric acid, if appropriate in the presence of oleum, attemperatures between 0° C. and 100° C.

2,3-Dichloro-2,3-difluoro- 1,4!-benzodioxane, of the formula (VII-1),was hitherto unknown. The compound can be prepared by reacting2,2,3,3-tetrachloro- 1,4!-benzodioxane, of the formula ##STR30## withanhydrous hydrofluoric acid in an autoclave at temperatures between -10°C. and +70° C. (cf. preparation examples).

Diluents which are suitable for carrying out the process according tothe invention are inert organic solvents. The following can preferablybe used: aliphatic, alicyclic or aromatic, optionally halogenatedhydrocarbons such as, for example, benzine, benzene, toluene, xylene,chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane,dichloromethane, chloroform or carbon tetrachloride; ethers such asdiethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethyleneglycol dimethyl ether or ethylene glycol diethyl ether, ketones such asacetone or butanone or methyl isobutyl ketone; nitriles such asacetonitrile, propionitrile or benzonitrile, or esters such as methylacetate or ethyl acetate.

The process according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all customary inorganic or organic bases. The following canpreferably be used: alkaline earth metal hydroxides or alkali metalhydroxides, such as sodium hydroxide, calcium hydroxide, potassiumhydroxide or else ammonium hydroxide, alkali metal carbonates, such assodium carbonate, potassium carbonate, potassium hydrogen carbonate,sodium hydrogen carbonate, alkali metal acetates or alkaline earth metalacetates, such as sodium acetate, potassium acetate or calcium acetate,and tertiary amines, such as trimethylamine, triethylamine,tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the process according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 150° C.,preferably at temperatures between 20° C. and 120° C.

The process according to the invention is normally carried out underatmospheric pressure. However, it is also possible to carry out theprocess under elevated or reduced pressure.

To carry out the process according to the invention, 1.0 to 2.0 mol,preferably 1.0 to 1.3 mol, of sulphonyl chloride of the formula (III)and, if appropriate, 1.0 to 2.0 mol, preferably 1.0 to 1.3 mol, ofreaction auxiliary are generally employed per mole of benzimidazole ofthe formula (II) in a diluent. The reaction is carried out and thereaction products are worked up and isolated by customary methods (cf.also preparation examples).

The active compounds of the formula (I) according to the invention havea potent action against pests and can be employed in practice forcontrolling undesirable harmful organisms. The active compounds aresuitable for use as crop protection agents, in particular as fungicides.

Fungicidal agents are employed in crop protection for controllingPlasmodiophoromycetes, Oemycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some pathogens causing fungal diseases which come under the genericnames listed above may be mentioned as examples, but not by way oflimitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Pseudoperonospora humuli orPseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechlera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellucularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of aerial parts of plants, of propagation stock and seeds, andof the soil.

In this context, the active compounds according to the invention can beemployed particularly successfully for controlling diseases in fruit andvegetable growing, such as, for example, against the pathogen causingtomato blight (Phytophthora infestans) or against the pathogen causingapple scab (Venturia inaequalis) or against the pathogen causing downymildew on grapevines (Plasmopara viticola) or for controlling ricediseases, such as, for example, against the pathogen causing rice blastdisease (Pyricularia oryzae).

Moreover, the active compounds according to the invention have a goodin-vitro activity.

In addition, the active compounds according to the invention aresuitable for controlling animal pests, preferably arthropods andnematodes, particularly insects and arachnida encountered inagriculture, in forests, in the protection of stored products andmaterials, and in the hygiene sector. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp..

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofinannophila pseudospretella,Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysiaambiguella, Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Bruchidius obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp:,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp..

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychusspp..

The plant-parasitic nematodes include Pratylenchus spp., Radopholussimilis, Ditylenchus dipsaci, Tulenchulus semipenetrans, Heteroderaspp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinemaspp. and Trichodorus spp.,

The active compounds of the formula (I) according to the invention arealso distinguished by an outstanding acaricidal activity, for exampleagainst the greenhouse red spider mite (Tetranychus urticae). They alsohave a good foliar-acting insecticidal activity.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted into the customary formulations, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, microcapsulations in polymeric substances and in coatingcompositions for seed, and ULV cold mist and warm mist formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants. If water is used as the extender, organic solvents can, forexample, also be used as auxiliary solvents. The following are mainlysuitable as liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, alcohols such as butanol or glycol andtheir ethers and esters, ketones such as acetone, methyl ethyl ketone,methyl iso-butyl ketone or cyclohexanone, strongly polar solvents suchas dimethylformamide and dimethyl sulphoxide, and water; liquefiedgaseous extenders or carriers are to be understood as meaning liquidswhich are gaseous at ambient temperature and under atmospheric pressure,for example aerosol propellants such as halogenohydrocarbons and butane,propane, nitrogen and carbon dioxide; suitable solid carriers are: forexample ground natural minerals such as kaolins, clays, talc, chalk,quartz, attapulgite, montmorillonite or diatomaceous earth, and groundsynthetic minerals such as highly-disperse silica, alumina andsilicates; suitable solid carriers for granules are: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, and also synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, maize cobs and tobacco stalks; suitable emulsifiers and/orfoam-formers are: for example non-ionic and anionic emulsifiers, such aspolyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates; suitabledispersants are: for example lignosulphite waste liquors andmethylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, and naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocynainedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

When used as fungicides, the active compounds according to theinvention, as such or in their formulations, can also be used as amixture with known fungicides, bactericides, acaricides, nematicides orinsecticides, for example to widen the spectrum of action or to preventthe build-up of resistance. In many cases, synergistic effects areobtained, i.e. the activity of the mixture is higher than the activityof the individual components.

Examples of particularly advantageous components in mixtures are thefollowing compounds:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2',6'-dibromo-2-methyl-4'-trifluoromethoxy4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl (E)-2-{2-6-(2-cyanophenoxy)-pyrimidin-4-yloxy!-phenyl}-3-methoxyacrylate; methyl(E)-methoximino- alpha-(o-tolyloxy)-o-tolyl!acetate; 2-phenylphenol(OPP), aldimorph, ampropylfos, anilazine, azaconazole,

benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetylaluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane,

kasugamycin, copper preparations such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,myclobutanil,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxycarboxin,

pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin,polyoxin, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil,pyroquilon,

quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,tridemorph, triflumizole, triforine, triticonazole,

validamycin A, vinclozolin,

zineb, ziram

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb,buprofezin, butocarboxin, butylpyridaben,

cadusafos, carbaryl, carbofuran; carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivemectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamdon, phoxim, piriniicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyradaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

When used as fungicides, the active compounds can be used as such, inthe form of their formulations or the use forms prepared therefrom, suchas ready-to-use solutions, suspensions, wettable powders, pastes,soluble powders, dusts and granules. They are used in the customarymanner, for example by pouring, spraying, atomizing, spreading, dusting,foaming, brushing on or the like.

It is furthermore possible to apply the active compounds by the ultralow volume method, or to inject the preparation of active compound, orthe active compound itself, into the soil. The seed of plants may alsobe treated.

In the treatment of potted plants, the active compound concentrations inthe use forms can be varied within a substantial range when used asfungicides. They are generally between 1 and 0.0001% by weight,preferably between 0.5 and 0.001%.

When used as fungicides, amounts of active compound of from 0.001 to 50g, preferably 0.01 to 10 g, are generally required per kilogram of seedin the case of seed treatment.

When used as fungicides, active compound concentrations of from 0.00001to 0.1% by weight, preferably from 0.0001 to 0.02%, are required at thesite of action in the case of soil treatment.

When used as insecticides and acaricides, the active compounds accordingto the invention, in their commercially available formulations and inthe use forms prepared from the formulations, may be present in the formof a mixture with other active compounds such as insecticides,attractants, sterilants, acaricides, nematicides, fungicides, growthregulators or herbicides. The insecticides include, for example,phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, and the like.

The following compounds may be mentioned:

acrinathrin, alphamethrin, betacyfluthrin, bifenthrin, brofenprox,cis-resmethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin,cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin,fenvalerate, flucythrinate, fluvalinate, lambdacyhalothrin, permethrin,pyresmethrin, pyrethrum, silafluofen, tralomethrin, zetamethrin,alanycarb, bendiocarb, benfuracarb, bufencarb, butocarboxim, carbaryl,cartap, ethiofencarb, fenobucarb, fenoxycarb, isoprocarb, methiocarb,methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, terbam,thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb,

acephate, azinphos A, azinphos M, bromophos A, cadusafos,carbophenothion, chlorfenvinphos, chlormephos, chlorpyrifos,chlorpyrifos M, cyanophos. Demeton M, demeton-S-methyl, demeton S,Diazinon, Dichlorvos, dicliphos, dichlorfenthion, dicrotophos,dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, ethion,etrimphos, fenitrothion, fenthion, fonophos, formothion, heptenophos,iprobenfos, isazophos, isoxathion, phorate, malathion, mecarbam,mervinphos, mesulfenphos, methacrifos, methamidophos, naled, omethoate,oxydemeton M, oxydeprofos, parathion A, parathion M, phenthoate,phorate, phosalone, phosmet, phosphamdon, phoxim, pirimiphos A,pirimiphos M, propaphos, prothiophos, prothoate, pyraclophos,pyridaphenthion, quinalphos, salithion, sebufos, sulfotep, sulprofos,tetrachlorvinphos, temephos, thiomethon, thionazin, trichlorfon,triazophos, vamidothion, buprofezin, chlorfluazuron, diflubenzuron,flucycloxuron, flufenoxuron, hexaflumuron, pyriproxifen, tebufenozide,teflubenzuron, triflumuron,

Imidacloprid, Nitenpyram, N-(6-chloro-3-pyridinyl)methyl!-N'-cyano-N-methyl-ethanimidamide (NI-25),

abamectin, amitrazin, avermectin, azadirachtin, bensultap, Bacillusthuringiensis, cyromazine, diafenthiuron, emamectin, ethofenprox,fenpyrad, fipronil, flufenprox, lufenuron, metaldehyd, milbemectin,pymetrozine, tebufenpyrad, triazuron, aldicarb, bendiocarb, benfuracarb,carbofuran, carbosulfan, chlorethoxyfos, cloethocarb, disulfoton,ethophrophos, etrimphos, fenamiphos, fipronil, fonofos, fosthiazate,furathiocarb, HCH, isazophos, isofenphos, methiocarb, monocrotophos,nitenpyram, oxamyl, phorate, phoxim, prothiofos, pyrachlofos, sebufos,silafluofen, tebupirimphos, tefluthrin, terbufos, thiodicarb, thiafenox,azocyclotin, butylpyridaben, clofentezine, cyhexatin, diafenthiuron,diethion, emamectin, fenazaquin, fenbutatin oxide, fenothiocarb,fenpropathrin, fenpyrad, fenpyfoximate, fluazinam, fluazuron,flucycloxuron, flufenoxuron, fluvalinate, fubfenprox, hexythiazox,ivemectin, methidathion, monocrotophos, moxidectin, naled, phosalone,profenofos, pyraclofos, pyridaben, pyrimidifen, tebufenpyrad,thuringiensin, triarathene and4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile(AC 303630).

When used as insecticides and acaricides, the active compounds accordingto the invention can furthermore be present in their commerciallyavailable formulations and in the use forms prepared from theseformulations in the form of a mixture with synergists. Synergists arecompounds by which the activity of the active compounds is increasedwithout it being necessary for the synergist added to be active itself.

When used as insecticides and acaricides, the active compound content ofthe use forms prepared from the conmmercially available formulations canvary within wide limits. The active compound concentration of the useforms can be from 0.0000001 up to 95% by weight of active compound,preferably between 0.0001 and 1% by weight.

They are applied in the customary manner adapted to suit one of the useforms.

Preparation and use of the active compounds according to the inventioncan be seen from the examples which follow.

PREPARATION EXAMPLES EXAMPLE 1 ##STR31##

4.6 g (15 mmol) of 2-cyano-6,7-dichloro-6,7-difluoro- 1,4!dioxino2,3-f!benzimidazole are added in portions with stirring at roomtemperature to a mixture of 0.6 g (1 5 mmol) of 60% sodium hydride in 70ml of tetrahydrofuran. Stirring is continued for 30 minutes at roomtemperature, 4.6 g (30 mmol) of methanesulphonyl chloride are thenadded, the mixture is refluxed for 12 hours.

After cooling, the solution is poured in 400 ml of water. The mixture isextracted three times using in each case 100 ml of methylene chloride,and, after drying, the combined organic extracts are concentrated under.reduced pressure. The residue obtained is subsequently crystallized bystirring with 20 ml of ether.

This gives 4.9 g (85% of theory) of2-cyano-6,7-dichloro-6,7-difluoro-3-methylsulphonyl- 1,4!dioxino2,3-f!benzimidazole of melting point 123° to 126° C.

Preparation of the Starting Materials ##STR32##

59.7 g (0.15 mol) of 6,7-dichloro-6,7-difluoro-2-trichloromethyl-1,4!dioxino 2,3-f!benzimidazole are added with stirring at roomtemperature to a mixture of 250 ml of concentrated aqueous ammoniasolution and 200 ml of ethanol.

The mixture is stirred for 20 hours at room temperature and thenacidified using hydrochloric acid. The reaction mixture is extractedthree times using in each case 150 ml of methylene chloride. The organicextracts are dried and concentrated. The residue obtained is thenpurified by chromatography and silica gel using diethyl ether as theeluent.

This gives 23.8 g (52% of theory) of 2-cyano-6,7-dichloro-6,7-difluoro-1,4!dioxino 2,3-f!benzimidazole of melting point >230° C. ##STR33##

54.0 g (0.3 mol) of methyl 2,2,2-trichloroacidimidate are added dropwisewith stirring at room temperature to a mixture of 54.2 g (0.20 mol) of6,7-diamino-2,3-dichlbro-2,3-difluoro- 1,4!-benzodioxane and 200 ml ofglacial acetic acid. After the addition has ended, stirring is continuedfor 20 hours at room temperature. 300 ml of water are then added, andthe resulting precipitate is filtered off and dried.

This gives 63.1 g (79% of theory) of6,7-dichloro-6,7-difluoro-2-trichloromethyl- 1,4!dioxino2,3-f!benzimidazole of melting point >230° C. ##STR34##

316 g (0.95 mol) of 2,3-dichloro-2,3-difluoro-6,7-dinitro-1,4!-benzodioxane in 1500 ml of tetrahydrofuran together with 30 g ofRaney nickel are introduced into a hydrogenating autoclave, and themixture is flushed with hydrogen and subsequently hydrogenated byinjecting 30 to 50 bar hydrogen at 25° to 45° C. When no more hydrogenis absorbed, the autoclave is cooled and the pressure is released. Thesolvent is distilled off after removal of the catalyst by filtration.

This gives 246 g of 6,7-diamino-2,3-dichloro-2,3-difluoro-1,4!-benzodioxane of melting point 130° to 131° C. ##STR35##

400 g of mixed acid (33% by weight of HNO₃, 67% by weight of H₂ SO₄) areintroduced into a stirred apparatus at 20° C., and 200 g of2,3-dichloro-2,3-difluoro-1,4-benzodioxane are added dropwise at roomtemperature with stirring. The mixture is stirred for 1 hour at 20° C.and then for 1 hour at 40° C. 100 ml of 20% oleum are then addeddropwise. Stirring is continued for 2 hours at 40° C. and then for 3hours at 50° C. After the mixture has cooled, it is transferred to 500 gof ice, and the product is taken up in dichloromethane. After washingwith water, the solution is dried and subsequently freed from solvent.

This gives 245 g of 2,3-dichloro-2,3-difluoro-6,7-dinitro-1,4!-benzodioxane ##STR36##

1800 ml of anhydrous hydrogen fluoride are introduced into afluorination apparatus, and 1300 g of 2,2,3,3-tetrachloro-1,4!-benzodioxane are introduced at -10° C. The autoclave is then sealedand the contents heated to 60° C., with stirring. After the evolution ofhydrogen chloride has ceased (pressure released by means of acondenser), the mixture is cooled, the hydrogen fluoride is distilledoff, and the residue is transferred onto ice. After phase separation,the organic product is dried and distilled.

This gives 665 g of 2,3-dichloro-2,3-difluoro-1,4-benzodioxane ofboiling point 82° to 83° C./18 mbar.

Example 2 ##STR37##

5.4 g (40 mmol) of pulverized potassium carbonate are added, at roomtemperature, to 5.4 g (20 mmol) of 2-cyano-6,6,7,7-tetrafluoro1,4!dioxino 2,3-f!benzimidazole in 100 ml of acetonitrile, 4.6 g (30mmol) of methanesulphonyl chloride are then added dropwise with stirringat room temperature, and, after the addition has ended, the mixture isrefluxed for 6 hours. The reaction mixture is subsequently cooled toroom temperature and poured into 500 ml of water. The mixture isextracted three times using in each case 150 ml of methylene chloride.The combined organic phases are dried over sodium sulphate and freedfrom solvent under reduced pressure.

This gives 5.5 g (79% of theory) of2-cyano-3-methylsulfonyl-6,6,7,7-tetrafluoro 1,4!dioxino2,3-f!benzimidazole of melting point 180° to 183° C.

The compounds of the formula listed in the table below are preparedanalogously to Examples 1 and 2 and following the general description ofthe process according to the invention.

    ______________________________________                                         ##STR38##                     (I)                                            Ex.                                            m.p.                           No   X.sup.1                                                                             X.sup.2                                                                             X.sup.3                                                                           X.sup.4                                                                           Z   R    Y            (°C.)                   ______________________________________                                        3    F     F     F   F   H   CN   C.sub.2 H.sub.5                                                                            177-84                         4    F     F     F   F   H   CN                                                                                  ##STR39##   153-57                         5    F     F     F   F   H   CN   CH.sub.2C(CH.sub.3)CH.sub.2                                                                 90-94                         6    F     F     F   F   H   CN   (CH.sub.2).sub.3 Cl                                                                        133-36                         ______________________________________                                    

Use Examples

The use examples which follow, the compounds given below were employedas parison substances. ##STR40##

(All disclosed in EP-A 0 517 476 or DE-OS (German. PublishedSpecification) 4 139 950).

Example A

Venturia test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism Venturia inaequalis andthen remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation takes place 12 days after the inoculation.

In this test, an efficacy of over 80% is shown, at an active compoundconcentration of 10 ppm, by the compounds of the formulae (I-1) and(1-2), while the comparison substances (A), (B) and (C) have an efficacyof 43%, 0% and 18%, respectively.

                                      TABLE A                                     __________________________________________________________________________    Venturia test (apple)/protective                                                                         Efficacy in % of the                                                          untreated control at an                                                       active compound                                                               concentration of 10 ppm                            Active ingredient          in the spray mixture                               __________________________________________________________________________     ##STR41##            (A) (known)                                                                        43                                                  ##STR42##            (B) (known)                                                                        0                                                   ##STR43##            (C)  18                                                  ##STR44##            (I-2)                                                                              99                                                  ##STR45##            (I-1)                                                                              84                                                 __________________________________________________________________________

Example B

Pyriculaia test (rice)/protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease level is carried out 4 days after theinoculation.

In this test, an efficacy of 90% is shown, as an active compoundconcentration of 0.025%, by the compound of the formula (I-2), while thecomparison substance (A) has an efficacy of 10%.

                                      TABLE B                                     __________________________________________________________________________    Pyricularia test (rice)/protective                                                                    Active compound                                                                       Efficacy in %                                                         concentration in                                                                      of the untreated                              Active compound         %       control                                       __________________________________________________________________________     ##STR46##          (A) (known)                                                                       0.025   10                                             ##STR47##          (I-2)                                                                             0.025   90                                            __________________________________________________________________________

Example C

Tetranychus test (OP resistant/immersion treatment)

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are severely infested with allstages of the greenhouse red spider mite Tetranychus urticae areimmersed in a preparation of the active compound of the desiredconcentration.

After the desired periods of time, the activity in % is determined. 100%means that all the spider mites have been killed; 0% means that none ofthe spider mites have been killed.

In this test, a degree of destruction of over 90% is shown, at an activecompound concentration of 0.001% after 13 days, by the compound of theformula (I-2), while the comparison substance (A) causes a degree ofdestruction of 60%.

                                      TABLE C                                     __________________________________________________________________________    Tetranychus test (OP resistant/immersion treatment)                                                   Active compound                                                                       Efficacy in %                                                         concentration in                                                                      of the untreated                              Active compound         %       control                                       __________________________________________________________________________     ##STR48##          (A) (known)                                                                       0.001   60                                             ##STR49##          (I-2)                                                                             0.001   98                                            __________________________________________________________________________

We claim:
 1. A compound of the formula: ##STR50##
 2. A process forpreparing a compound according to claim 1, said process comprisingreacting 6,7-dichloro-6,7-difluoro-2-trichloromethyl- 1,4!-dioxino-2,3-f!-benzimidazole, which has the formula: ##STR51## with an aqueousammonia solution in the presence of a diluent.